Preparation of polymer complexes with π-conjugated polymer ligands and control of catalytic functionalities

π-共轭聚合物配体聚合物配合物的制备及催化功能的控制

• 批准号: 13555258
• 负责人: YAMAMOTO Takakazu
• 金额: $ 8.13万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13555258/
• 关键词: Organometallic chemistry; Polycondensation; π-Conjugated; Conductive polymer; Polymer ligand; Polymer metal complex; Catalytic activity; Optical functionalities; 触媒特性; 機能制御

Various it-conjugated polymer ligands have been prepared by using organometallic coupling reactions such as Ni-and Pd-complex mediated C-C coupling. The obtained polymer ligands were constituted of coordinating units such as pyridine, 2,2'-bipyridyl, 1,10-phenanthroline, biimidazole, 8-quinolinol, 2,2'-bithiaziazole, and Salen type ligand. According to expansion of the it-conjugation system, the polymers showed shifts of the UV-vis absorption peak of the unit to a longer wavelength. The it-conjugated polymer ligands form various metal complexes on addition of metal species such as Cu(II), Ni(II), Ru(II), and Zn(II) compounds. On the complex formation, changes in the UV-vis absorption spectra were observed. The metal complexes often showed photoluminescence. The metal complexes also showed functionalities such as (1)electrochemical activity which were expected to he related electrocatalytic reactions, (2)optical functionalities, and (3)electrical conductivity. Some complexes are known to serve as catalysts for photoevolution of H_2 from aqueous media and for redox reactions.

各种it-共轭聚合物配体已通过使用有机金属偶联反应（例如Ni-和Pd-络合物介导的C-C偶联）制备。所得聚合物配体由吡啶、2，2'-联吡啶、1，10-菲咯啉、联咪唑、8-喹啉、2，2'-联噻唑、Salen型配体等配位单元构成。根据it-共轭体系的扩展，聚合物表现出单元的紫外-可见吸收峰向更长波长的移动。 π-共轭聚合物配体在添加金属物质（例如 Cu(II)、Ni(II)、Ru(II) 和 Zn(II) 化合物）时形成各种金属配合物。关于络合物的形成，观察到紫外-可见吸收光谱的变化。金属配合物经常表现出光致发光。金属配合物还表现出诸如（1）电化学活性（预计与电催化反应相关）、（2）光学功能和（3）导电性等功能。已知一些配合物可用作从水介质中光析出 H_2 和氧化还原反应的催化剂。

项目成果

Bang-Lin Lee: "Synthesis of Light-emitting π-Conjugated Poly(pyrimido[5,4-d]-pyrimidine-2.6-diyl) with Bulky Side Chains and High Molecular Weight"Polymer. 43. 4531-4534 (2002)

Bang-Lin Lee：“具有大体积侧链和高分子量的发光 π-共轭聚（嘧啶并[5,4-d]-嘧啶-2.6-二基）的合成”聚合物 43. 4531-4534 (2002)。

Takakazu Yamamoto: "Neutral Poly(3.4-ethylenedioxythiophene-2,5-diyl)s : Preparation by Organometallic Polycondensation and their Unique p-doping Behavior"Polymer. 43. 711-719 (2002)

Takakazu Yamamoto：“中性聚（3.4-乙撑二氧噻吩-2,5-二基）：通过有机金属缩聚制备及其独特的 p 掺杂行为”聚合物。

Takakazu Yamamoto: "Synthesis and Chemical Properties of π-Conjugated Poly(Imidazole-2.5-diyl)s"Macromolecules. 36. 1047-1053 (2003)

Takakazu Yamamoto：“π-共轭聚（咪唑-2.5-二基）的合成和化学性质”36。1047-1053（2003）。

Takakazu Yamamoto: "Cross-coupling Reactions for Preparation of π-Conjugated Polymers"J. Organometal. Chem.. 653. 195-199 (2002)

Takakazu Yamamoto：“制备 π 共轭聚合物的交叉偶联反应”J. Organometal。 653. 195-199 (2002)

T.Yamamoto, M.Arai, H.Kokubo, S.Sasaki: "Comparison of Organometallic Copolymerization of Thiophene with 4-Alkylthiazole and 3-Alkylthiophene. Control of Regioregularity in the Copolymerization with 4-Alkyithiazole"J.Polym.Sci.Part A : Polym.Chem.. 41. 14

T.Yamamoto、M.Arai、H.Kokubo、S.Sasaki：“噻吩与 4-烷基噻唑和 3-烷基噻吩的有机金属共聚反应的比较。与 4-烷基噻唑共聚过程中区域规整性的控制”J.Polym.Sci.Part